CN101133059A - 5,6-dialkyl-7-amino-azolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds - Google Patents

Abstract

The invention relates to 5,6-dialkyl-7-amino-azolopyrimidines of formula (I), in which the substituents are defined as follows: R<1> represents haloalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl; R<2> represents alkyl, alkoxyalkyl, alkenyl or alkynyl, where R<1> and/or R<2> can be substituted as per the description; A represents N or CH; and R<3> represents CH3 and if A represents CH additionally hydrogen. The invention also relates to a method and intermediate products for producing said compounds, to agents containing the latter and to the use of the compounds for controlling plant pathogenic fungi.

Description

5,6-dialkyl group-7-amino azoles and pyrimidine, its preparation method and the purposes in controlling pathogenic fungi by means thereof and comprise these compound compositions

The present invention relates to 5 of formula I, amino azoles of 6-dialkyl group-7-and pyrimidine:

Wherein each substituting group is following defines:

R ¹Be C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain is not substituted and maybe can has 1-3 identical or different radicals R ^aAnd/or R ^bOr

Be C ₁-C ₁₄Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₁-C ₆Alkoxy-C ₂-C ₁₂Alkenyl or C ₁-C ₆Alkoxy-C ₂-C ₁₂Alkynyl, wherein carbochain can have 1-3 identical or different radicals R ^a

R ^aBe halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkylthio, C ₃-C ₁₂Alkenyloxy, C ₃-C ₁₂Alkynyloxy group, NR ¹¹R ¹², or

For having 1-4 identical or different radicals R ^bC ₃-C ₆Cycloalkyl;

R ^bBe C ₁-C ₄Alkyl, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₆Alkenyloxy, C ₃-C ₆Alkynyloxy group and NR ¹¹R ¹²,

R ¹¹, R ¹²Be hydrogen or C ₁-C ₆Alkyl;

Radicals R wherein ^aCarbochain itself can be by halo;

R ²Be C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain can be by 1-3 radicals R ^cReplace:

R ^cBe halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₁₂Alkenyloxy, C ₃-C ₁₂Alkynyloxy group, NR ¹¹R ¹²Maybe can have 1-4 identical or different group C ₁-C ₄Alkyl, halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₆Alkenyloxy, C ₃-C ₆Alkynyloxy group or NR ¹¹R ¹²C ₃-C ₆Cycloalkyl; A is N or CH; With

R ³Be CH ₃And if A is CH, then R ³Extra is hydrogen.

In addition, the present invention relates to prepare the method for these compounds, the composition that comprises them and their purposes in control plant-pathogenic harmful fungoid.

5,6-dialkyl group-7-aminotriazole also-and-pyrazolopyrimidine proposes in GB 1 148 629 with general fashion.5 of various Fungicidally actives, 6-dialkyl group-7-aminotriazole also-and-pyrazolopyrimidine is known by EP-A 141 317.Yet they is active and unsatisfactory in many cases.Based on this, the purpose of this invention is to provide compound with improved activity and/or wideer activity profile.

We find that this purpose is realized by the defined compound of beginning.In addition, we have found to prepare the method and the intermediate of these compounds, the composition that comprises them and use Compound I methods for fighting harmful mushrooms.

Those compounds in formula I compound and the above-mentioned publication different are the substituent specific embodiments in 6 on azoles and pyrimidine skeleton, and this substituting group constitutes haloalkyl or unsaturated aliphatic group.

Compare with known compound, formula I compound is more effective to harmful fungoid.

The compounds of this invention can obtain by different approaches.Advantageously the amino azoles reaction of replacement beta-ketoester by making formula II and formula III obtains The compounds of this invention with 7-hydroxyl azoles and the pyrimidine that obtains formula IV.Variable among formula II and the IV as formula I is defined and formula II in radicals R be C ₁-C ₄Alkyl; For actual cause, preferable methyl, ethyl or propyl group here.

Formula IV compound is new.

The reaction of the replacement beta-ketoester of formula II and the amino azoles of formula III can be carried out in the solvent existence or not.Advantageously use and raw material is inertia and raw material substantially dissolves in wherein solvent wholly or in part.Suitable solvent is alcohols especially, as ethanol, propyl alcohol, butanols, glycol or glycol monoether, glycol ether or its monoether, aromatic hydrocarbons is as toluene, benzene or 1,3, the 5-Three methyl Benzene, amides is as dimethyl formamide, diethylformamide, dibutyl formamide, N, the N-N,N-DIMETHYLACETAMIDE, the lower alkanols alkanoic acid is as formic acid, acetate, propionic acid, or bases, as basic metal and alkaline earth metal hydroxides, basic metal and alkaline earth metal oxide, basic metal and alkaline earth metal hydride, alkali metal ammonia compound, basic metal and alkaline earth metal carbonate, also has alkali metal hydrocarbonate, organometallic compound, especially basic metal alkylate, alkyl halide magnesium, basic metal and alkaline-earth alkoxides and dimethoxy magnesium, also has organic bases, tertiary amine for example is as Trimethylamine 99, triethylamine, the triisopropyl ethylamine, Tributylamine and N-methyl piperidine, N-methylmorpholine, pyridine, the pyridine that replaces is as collidine, lutidine and 4-dimethylaminopyridine, and the mixture of Wyovin and these solvents and water.Appropriate catalyst is aforesaid alkali or acid, as sulfonic acid or mineral acid.This reaction is carried out under the solvent or is carried out in chlorobenzene, dimethylbenzene, methyl-sulphoxide or N-Methyl pyrrolidone particularly preferably in not having.Particularly preferred alkali is tertiary amine, as triisopropylamine, Tributylamine, N-methylmorpholine or N-methyl piperidine.If this is reflected in the solution and carries out, then temperature is 50-300 ℃, preferred 50-180 ℃ [referring to EP-A 770 615; Adv.Het.Chem., the 57th volume (1993), the 81st page reaches each page subsequently].

Alkali uses with catalytic amount usually; Yet they can also equimolar amount or excessive use or suitable for solvent.

The condenses of gained formula IV in most of the cases precipitates from reaction soln with respective pure form and makes they and halide reagent after with same solvent or water washing and subsequent drying, especially chlorination or bromide reagent reaction, obtain formula V compound, wherein Hal is chlorine or bromine, especially chlorine.Preferred chlorination reagent such as phosphoryl chloride, thionyl chloride or the SULPHURYL CHLORIDE used of this reaction carried out under 50-150 ℃, preferably carries out under reflux temperature in excessive phosphorus chloride.After the evaporation excessive phosphorus chloride, handle resistates with frozen water, suitable words add not and water-soluble mixed solvent.Suitable words after the evaporation inert solvent by the isolating chlorizate of exsiccant organic phase in most of the cases very pure and subsequently with ammonia in inert solvent in 100-200 ℃ of down reaction, obtain also [1,5-a] pyrimidine of 7-amino azoles.The preferred molar excess 1-10 ammonia doubly that uses of this reaction carries out under the pressure of 1-100 crust.

Suitable words are after evaporating solvent, and the amino azoles of 7-of the present invention also [1,5-a] pyrimidine separates with crystalline compounds by digestion in water.

The beta-ketoester of formula II can be as Organic Synthesis Coll., the 1st volume, the 248th page of described preparation and/or can be commercial.

The intermediate of formula V is new.

Perhaps can be by making wherein R ¹And R ²The amino azoles of the substituted acyl prussiate of formula VI and formula III reaction and obtain formula I compound of the present invention as defined above.

This reaction can be carried out in the solvent existence or not.Advantageously use raw material that it is inertia substantially and dissolve in wherein solvent wholly or in part.Suitable solvent especially is an alcohols, as ethanol, propyl alcohol, butanols, glycol or glycol monoether, glycol ether or its monoether, aromatic hydrocarbons, as toluene, benzene or 1,3,5-Three methyl Benzene, amides, as dimethyl formamide, diethylformamide, dibutyl formamide, N, the N-N,N-DIMETHYLACETAMIDE, the lower alkanols alkanoic acid is as formic acid, acetate, propionic acid, or aforesaid alkali, and the mixture of these solvents and water.If be reflected in the solution and carry out, then temperature of reaction is 50-300 ℃, preferred 50-150 ℃.

Suitable words are after evaporating solvent or dilute with water, and the amino azoles of the 7-of formula I of the present invention also [1,5-a] pyrimidine separates with crystalline compounds.

Amino azoles of some preparation 7-also [1,5-a] the substituted alkyl prussiate of the required formula VI of pyrimidine is known or can uses highly basic such as alkalimetal hydride, alkali metal alcoholates, alkali metal ammonia compound or metal alkyl compound preparation [referring to J.Amer.Chem.Soc. by alkyl prussiate and carboxylicesters by currently known methods, the 73rd volume (1951), the 3766th page].

R wherein ¹Be C ₁-C ₁₄Haloalkyl, C ₁-C ₁₂Halogenated alkoxy-C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Haloalkyl, C ₂-C ₁₂Halogenated alkenyl or C ₂-C ₁₂The formula I compound of halo alkynyl can obtain by azoles and the pyrimidine of the corresponding formula VII of halogenation:

In formula VII, R is C ₁-C ₁₄Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl, C ₂-C ₁₂Alkynyl, wherein carbochain can have 1-3 radicals R ^a

Halogenation is usually at 0-200 ℃; in inert organic solvents, in the presence of radical initiator (for example dibenzoyl peroxide or Diisopropyl azodicarboxylate or under the UV radiation of for example using the Hg mercury vapo(u)r lamp) or acid, carry out under preferred 20-110 ℃ the temperature [referring to Synthetic Reagents; the 2nd volume; the 1-63 page or leaf; Verlag Wiley, New York (1974)].

Reactive component reacts to each other with equimolar amount usually.With regard to productive rate, maybe advantageously use excessive halide reagent based on VII.

Suitable halide reagent for example is elemental halogen (Cl for example ₂, Br ₂, I ₂), N-bromosuccinimide, N-chlorosuccinimide or dibromodimethyl hydantoin (dibromodimethyl-hydrantoin).Halide reagent is used as solvent with equimolar amount, excessive use or suitable words usually.

Some prepares the azoles of the required formula VII of above-claimed cpd I and pyrimidine is known or this can prepare [referring to EP-A 141 317] by currently known methods.

If each Compound I can not obtain by above-mentioned approach, then can prepare them by deriving of other Compound I.

Each isomer obtains isomer mixture if synthesize, then needn't separate usually, because can transform in the last handling process of using or in application in some cases mutually in (for example under the effect of light, acid or alkali).Such conversion also can take place after use, for example when handling plant, in the plant of handling or take place in harmful fungoid to be prevented and treated.

In the definition of symbol that following formula is given, use the collectivity term that is generally following substituent representative:

Halogen: fluorine, chlorine, bromine and iodine, especially fluorine or chlorine;

Alkyl: have the saturated straight chain or the branched hydrocarbyl radical of 1-4,1-6, a 1-8 or 1-10 carbon atom, for example C ₁-C ₆Alkyl, as methyl, ethyl, propyl group, the 1-methylethyl, butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, amyl group, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methyl-propyl;

Haloalkyl: have the straight chain or the branched-alkyl (as mentioned above) of 1-2, a 1-4 or 1-6 carbon atom, wherein the some or all hydrogen atoms in these groups can be substituted by above-mentioned halogen atom: C especially ₁-C ₂Haloalkyl, as chloromethyl, brooethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, chlorine methyl fluoride, dichloro one methyl fluoride, a chlorodifluoramethyl-, 1-chloroethyl, 1-bromotrifluoromethane, 1-fluoro ethyl, 2-fluoro ethyl, 2,2-two fluoro ethyls, 2,2,2-trifluoroethyl, 2-chloro-2-fluoro ethyl, 2-chloro-2,2-two fluoro ethyls, 2,2-two chloro-2-fluoro ethyls, 2,2,2-three chloroethyls, pentafluoroethyl group or 1,1,1-trifluoropropyl-2-base;

Alkenyl: have the unsaturated straight chain or the branched hydrocarbyl radical of 2-4,2-6, a 2-8 or 2-10 carbon atom and one or two two keys at an arbitrary position, for example C ₂-C ₆Alkenyl, as vinyl, the 1-propenyl, the 2-propenyl, the 1-methyl ethylene, the 1-butylene base, crotyl, the 3-butenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, the 1-pentenyl, pentenyl, the 3-pentenyl, the 4-pentenyl, 1-methyl isophthalic acid-butenyl, the 2-methyl-1-butene thiazolinyl, the 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, the 1-hexenyl, the 2-hexenyl, the 3-hexenyl, the 4-hexenyl, the 5-hexenyl, 1-methyl-1-pentene thiazolinyl, 2-methyl-1-pentene thiazolinyl, 3-methyl-1-pentene thiazolinyl, the 4-methyl-1-pentene base, 1-methyl-pentenyl, 2-methyl-pentenyl, 3-methyl-pentenyl, 4-methyl-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-crotyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butylene base, 1,2-dimethyl-crotyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butylene base, 1,3-dimethyl-crotyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butylene base, 2,3-dimethyl-crotyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butylene base, 3,3-dimethyl-crotyl, 1-ethyl-1-butylene base, 1-ethyl-crotyl, 1-ethyl-3-butenyl, 2-ethyl-1-butylene base, 2-ethyl-crotyl, 2-ethyl-3-butenyl, 1,1,2-trimethylammonium-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl isophthalic acid-propenyl and 1-ethyl-2-methyl-2-propenyl;

Alkoxyalkyl: by Sauerstoffatom saturated straight chain or single branching, two branching or three branching hydrocarbon chain, for example C at interval ₅-C ₁₂Alkoxyalkyl: can be by Sauerstoffatom at interval above-mentioned hydrocarbon chain at an arbitrary position with 5-12 carbon atom, as the propoxy-ethyl, butoxyethyl group, the pentyloxy ethyl, the hexyloxy ethyl, heptan oxygen base ethyl, the octyloxy ethyl, the ninth of the ten Heavenly Stems oxygen base ethyl, 3-(3-ethyl hexyl oxy) ethyl, 3-(2,4, the 4-trimethylpentyloxy) ethyl, 3-(1-ethyl-3-methyl butoxy) ethyl, ethoxycarbonyl propyl, the propoxy-propyl group, the butoxy propyl group, the pentyloxy propyl group, the hexyloxy propyl group, heptan oxygen base propyl group, the octyloxy propyl group, the ninth of the ten Heavenly Stems oxygen base propyl group, 3-(3-ethyl hexyl oxy) propyl group, 3-(2,4, the 4-trimethylpentyloxy) propyl group, 3-(1-ethyl-3-methyl butoxy) propyl group, the oxyethyl group butyl, the propoxy-butyl, the butoxy butyl, the pentyloxy butyl, the hexyloxy butyl, heptan oxygen Ji Dingji, the octyloxy butyl, the ninth of the ten Heavenly Stems oxygen Ji Dingji, 3-(3-ethyl hexyl oxy) butyl, 3-(2,4, the 4-trimethylpentyloxy) butyl, 3-(1-ethyl-3-methyl butoxy) butyl, the methoxyl group amyl group, the oxyethyl group amyl group, the propoxy-amyl group, the butoxy amyl group, the pentyloxy amyl group, the hexyloxy amyl group, heptan oxygen base amyl group, 3-(3-methyl hexyloxy) amyl group, 3-(2,4-dimethyl pentyloxy) amyl group, 3-(1-ethyl-3-methyl butoxy) amyl group;

Halogenated alkenyl: unsaturated straight chain or branched hydrocarbyl radical (as mentioned above) with 2-10 carbon atom and one or two two keys at an arbitrary position, wherein the some or all hydrogen atoms in these groups can be by above-mentioned halogen atom, and especially fluorine, chlorine and bromine substitute;

Alkynyl: have the straight chain or the branched hydrocarbyl radical of 2-4,2-6, a 2-8 or 2-10 carbon atom and one or two three key at an arbitrary position, for example C ₂-C ₆Alkynyl, as ethynyl, the 1-proyl, 2-propynyl, the ethyl acetylene base, the 2-butyne base, the 3-butynyl, 1-methyl-2-propynyl, the 1-pentynyl, the valerylene base, the 3-pentynyl, the 4-pentynyl, 1-methyl-2-butyne base, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl isophthalic acid-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexin base, 2-hexin base, 3-hexin base, 4-hexin base, 5-hexin base, 1-methyl-valerylene base, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentene alkynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentene alkynyl, 4-methyl-valerylene base, 1,1-dimethyl-2-butyne base, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-ethyl acetylene base, 1-ethyl-2-butyne base, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

Cycloalkyl: have 3-6 carbocyclic ring member's monocycle or dicyclo saturated hydrocarbyl, as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The scope of the invention comprises (R) of the formula I compound with chiral centre and (S) isomer and racemic modification.

Consider the purposes that is intended to of the azoles of formula I and pyrimidine, the following definition of special preferred substituents, in each case alone or in combination:

Preferred radicals R wherein ¹Has the Compound I of 9 carbon atoms at the most.

Equally preferred R wherein ¹Compound I for the haloalkyl of straight chain or single branching, two branching, three branching or more multiple branching.

In the embodiment of The compounds of this invention I, R ¹Be C ₁-C ₁₄Haloalkyl, C ₁-C ₁₂Halogenated alkoxy-C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Haloalkyl, C ₂-C ₁₂Halogenated alkenyl or C ₂-C ₁₂Halo alkynyl, these groups have 1 or 2 halogen atom.Here preferred C ₁-C ₉Halogenated alkoxy propyl group and C ₁-C ₉The halogenated alkoxy propyl group.

In another embodiment of Compound I, R ¹Be group C ₁-C ₁₄Haloalkyl, C ₁-C ₁₂Halogenated alkoxy-C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Haloalkyl, C ₂-C ₁₂Halogenated alkenyl or C ₂-C ₁₂The halo alkynyl, these groups contain halogen atom, and preferred halogen atom is positioned on the alpha-carbon atom.

In addition, be preferably as follows formula I compound, wherein R ¹Be group (CH ₂) _nCF ₃Or CH (CH ₃) (CH ₂) _mCF ₃, wherein n is that number and the m of 0-13 are the number of 0-11.

Be preferably as follows Compound I especially, wherein R ¹Be chloromethyl, brooethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, the chlorine methyl fluoride, dichloro one methyl fluoride, one chlorodifluoramethyl-, the 1-chloroethyl, the 1-bromotrifluoromethane, the 1-fluoro ethyl, the 2-fluoro ethyl, 2,2-two fluoro ethyls, 2,2, the 2-trifluoroethyl, 2-chloro-2-fluoro ethyl, 2-chloro-2,2-two fluoro ethyls, 2,2-two chloro-2-fluoro ethyls, 2,2,2-three chloroethyls, pentafluoroethyl group, 1,1,1-trifluoropropyl-2-base, the 1-chloropropyl, the 1-fluoropropyl, the 3-chloropropyl, the 3-fluoropropyl, 3,3, the 3-trifluoro propyl, the 1-chlorobutyl, 1-fluorine butyl, the 4-chlorobutyl, 4-fluorine butyl, 4,4,4-trifluoro butyl, 1-chlorine amyl group, 1-fluorine amyl group, 5,5,5-trifluoro amyl group, 5-chlorine amyl group, 5-fluorine amyl group, 1-chlorine hexyl, 1-fluorine hexyl, 6-chlorine hexyl, 6-fluorine hexyl, 6,6,6-trifluoro hexyl, 1-chlorine heptyl, 1-fluorine heptyl, 7-chlorine heptyl, 7-fluorine heptyl, 7,7,7-trifluoro heptyl, 1-chlorine octyl group, 1-fluorine octyl group, 8-fluorine octyl group, 8,8,8-trifluoro octyl group, 1-chlorine nonyl, 1-fluorine nonyl, 9-fluorine nonyl, 9,9,9-trifluoro nonyl, 9-chlorine nonyl, 1-fluorine decyl, 1-chlorine decyl, 10-fluorine decyl, 10,10,10-trifluoro decyl, 10-chlorine decyl, 1-chloro-undecane base, 1-fluorine undecyl, 11-chloro-undecane base, 11-fluorine undecyl, 11,11,11-trifluoro undecyl, 1-chlorododecane base, 1-fluorine dodecyl, 12-chlorododecane base, 12-fluorine dodecyl or 12,12,12-trifluoro dodecyl.

In another embodiment of Compound I, R ¹Be C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain is not substituted and maybe can has 1-3 identical or different radicals R ^aAnd/or R ^b

In the preferred embodiment of formula I compound, radicals R ^aDo not exist.

Especially preferred R wherein ¹And R ²Carbochain have the Compound I of 14 carbon atoms at the most together.

In the embodiment of The compounds of this invention I, R ²Be methyl, ethyl, n-propyl or normal-butyl, preferable methyl or ethyl, especially ethyl.

Radicals R ¹And/or R ²In halogen atom be preferably placed on the alpha-carbon atom.

R ¹And/or R ²In cyano group be preferably placed on the terminal carbon.

In another preferred embodiment of formula I compound, radicals R ^bDo not exist.

An embodiment of The compounds of this invention relates to wherein, and A is the Compound I of CH.These compounds are corresponding to formula I.1:

Another embodiment of The compounds of this invention relates to wherein, and A is the Compound I of N.These compounds are corresponding to formula I.2:

Especially consider its application, preferably be compiled in the Compound I in the following table.In addition, substituting group is mentioned in the his-and-hers watches group this as described substituent particularly preferred embodiment, and irrelevant with the combination of wherein mentioning them.

Table 1

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be methyl and R ³Be the formula of hydrogen compound I.1

Table 2

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be ethyl and R ³Be the formula of hydrogen compound I.1

Table 3

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be n-propyl and R ³Be the formula of hydrogen compound I.1

Table 4

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be sec.-propyl and R ³Be the formula of hydrogen compound I.1

Table 5

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be normal-butyl and R ³Be the formula of hydrogen compound I.1

Table 6

R wherein ¹For delegation and the R of each compound corresponding to Table A ²And R ³Be the formula of methyl compound I.1

Table 7

Wherein R1 is for the delegation of each compound corresponding to Table A, R ²Be ethyl and R ³Be the formula of methyl compound I.1

Table 8

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be n-propyl and R ³Be the formula of methyl compound I.1

Table 9

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be sec.-propyl and R ³Be the formula of methyl compound I.1

Table 10

R wherein ¹For the delegation of each compound corresponding to Table A, R ²Be normal-butyl and R ³Be the formula of methyl compound I.1

Table 11

R wherein ¹For delegation and the R of each compound corresponding to Table A ²Be the formula of methyl compound I.2

Table 12

R wherein ¹For delegation and the R of each compound corresponding to Table A ²Be the formula of ethyl compound I.2

Table 13

R wherein ¹For delegation and the R of each compound corresponding to Table A ²Be the formula of n-propyl compound I.2

Table 14

R wherein ¹For delegation and the R of each compound corresponding to Table A ²Be the formula of sec.-propyl compound I.2

Table 15

R wherein ¹For delegation and the R of each compound corresponding to Table A ²Be the formula of normal-butyl compound I.2

Table A

Sequence number	R 1
		A-1	CH 2F
A-2	CH 2Cl
		A-3	CHF 2
A-4	CHCl 2
		A-5	CF 3
A-6	CCl 3
		A-7	CHFCH 3
A-8	CHClCH 3
		A-9	CH 2CH 2F
A-10	CH 2CH 2Cl
		A-11	CCl 2CH 3
A-12	CF 2CH 3
		A-13	CH 2CHF 2
A-14	CH 2CHCl 2
		A-15	CH 2CF 3
A-16	CH 2CCl 3
		A-17	CF 2CF 3
A-18	CCl 2CCl 3
		A-19	CHFCH 2CH 3
A-20	CHClCH 2CH 3
		A-21	CH 2CHFCH 3
A-22	CH 2CHClCH 3
		A-23	CH 2CH 2CH 2F
A-24	CH 2CH 2CH 2Cl
		A-25	CCl 2CH 2CH 3
A-26	CF 2CH 2CH 3
		A-27	CH 2CH 2CHF 2
A-28	CH 2CH 2CHCl 2
		A-29	CH 2CH 2CF 3
A-30	CH 2CH 2CCl 3
		A-31	CF 2CF 2CF 3
A-32	CCl 2CCl 2CCl 3
		A-33	CH(CH 3)CF 3
A-34	CH(CH 3)CH 2F
		A-35	CH(CH 3)CH 2Cl
A-36	CH(CH 3)CHF 2

Sequence number	R 1
		A-37	CH(CH 3)CHCl 2
A-38	CH(CH 2F) 2
		A-39	CH(CH 2Cl) 2
A-40	CH(CHF 2) 2
		A-41	CH(CHCl 2) 2
A-42	CHFCH 2CH 2CH 3
		A-43	CHClCH 2CH 2CH 3
A-44	CH 2CHFCH 2CH 3
		A-45	CH 2CHClCH 2CH 3
A-46	CH 2CH 2CHFCH 3
		A-47	CH 2CH 2CHClCH 3
A-48	CH 2CH 2CH 2CH 2F
		A-49	CH 2CH 2CH 2CH 2Cl
A-50	CCl 2CH 2CH 2CH 3
		A-51	CF 2CH 2CH 2CH 3
A-52	CH 2CH 2CH 2CHF 2
		A-53	CH 2CH 2CH 2CHCl 2
A-54	CH 2CH 2CH 2CF 3
		A-55	CH 2CH 2CH 2CCl 3
A-56	CF 2CF 2CF 2CF 3
		A-57	CCl 2CCl 2CCl 2CCl 3
A-58	CH(CH 3)CH 2CH 2F
		A-59	CH(CH 3)CH 2CH 2Cl
A-60	CH(CH 3)CH 2CF 3
		A-61	CHFCH 2CH 2CH 2CH 3
A-62	CHClCH 2CH 2CH 2CH 3
		A-63	CH 2CHFCH 2CH 2CH 3
A-64	CH 2CHClCH 2CH 2CH 3
		A-65	CH 2CH 2CHFCH 2CH 3
A-66	CH 2CH 2CHClCH 2CH 3
		A-67	CH 2CH 2CH 2CHFCH 3
A-68	CH 2CH 2CH 2CHClCH 3
		A-69	CH 2CH 2CH 2CH 2CH 2F
A-70	CH 2CH 2CH 2CH 2CH 2Cl
		A-71	CCl 2CH 2CH 2CH 2CH 3
A-72	CF 2CH 2CH 2CH 2CH 3
		A-73	CH 2CH 2CH 2CH 2CHF 2
A-74	CH 2CH 2CH 2CH 2CHCl 2

Sequence number	R 1
		A-75	CH 2CH 2CH 2CH 2CF 3
A-76	CH 2CH 2CH 2CH 2CCl 3
		A-77	CF 2CF 2CF 2CF 2CF 3
A-78	CCl 2CCl 2CCl 2CCl 2CCl 3
		A-79	CH(CH 3)CH 2CH 2CH 2F
A-80	CH(CH 3)CH 2CH 2CH 2Cl
		A-81	CH(CH 3)CH 2CH 2CF 3
A-82	CHFCH 2CH 2CH 2CH 2CH 3
		A-83	CHClCH 2CH 2CH 2CH 2CH 3
A-84	CH 2CHFCH 2CH 2CH 2CH 3
		A-85	CH 2CHClCH 2CH 2CH 2CH 3
A-86	CH 2CH 2CHFCH 2CH 2CH 3
		A-87	CH 2CH 2CHClCH 2CH 2CH 3
A-88	CH 2CH 2CH 2CHFCH 2CH 3
		A-89	CH 2CH 2CH 2CHClCH 2CH 3
A-90	CH 2CH 2CH 2CH 2CHFCH 3
		A-91	CH 2CH 2CH 2CH 2CHClCH 3
A-92	CH 2CH 2CH 2CH 2CH 2CH 2F
		A-93	CH 2CH 2CH 2CH 2CH 2CH 2Cl
A-94	CCl 2CH 2CH 2CH 2CH 2CH 3
		A-95	CF 2CH 2CH 2CH 2CH 2CH 3
A-96	CH 2CH 2CH 2CH 2CH 2CHF 2
		A-97	CH 2CH 2CH 2CH 2CH 2CHCl 2
A-98	CH 2CH 2CH 2CH 2CH 2CF 3
		A-99	CH 2CH 2CH 2CH 2CH 2CCl 3
A-100	CF 2CF 2CF 2CF 2CF 2CF 3
		A-101	CCl 2CCl 2CCl 2CCl 2CCl 2CCl 3
A-102	CH(CH 3)CH 2CH 2CH 2CH 2F
		A-103	CH(CH 3)CH 2CH 2CH 2CH 2Cl
A-104	CH(CH 3)CH 2CH 2CH 2CF 3
		A-105	CHFCH 2CH 2CH 2CH 2CH 2CH 3
A-106	CHClCH 2CH 2CH 2CH 2CH 2CH 3
		A-107	CH 2CHFCH 2CH 2CH 2CH 2CH 3
A-108	CH 2CHClCH 2CH 2CH 2CH 2CH 3
		A-109	CH 2CH 2CH 2CHFCH 2CH 2CH 3
A-110	CH 2CH 2CH 2CHClCH 2CH 2CH 3
		A-111	CH 2CH 2CH 2CH 2CHFCH 2CH 3
A-112	CH 2CH 2CH 2CH 2CHClCH 2CH 3

Sequence number	R 1
		A-113	CH 2CH 2CH 2CH 2CH 2CHFCH 3
A-114	CH 2CH 2CH 2CH 2CH 2CHClCH 3
		A-115	CH 2CH 2CH 2CH 2CH 2CH 2CH 2F
A-116	CH 2CH 2CH 2CH 2CH 2CH 2CH 2Cl
		A-117	CCl 2CH 2CH 2CH 2CH 2CH 2CH 3
A-118	CF 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-119	CH 2CH 2CH 2CH 2CH 2CH 2CHF 2
A-120	CH 2CH 2CH 2CH 2CH 2CH 2CHCl 2
		A-121	CH 2CH 2CH 2CH 2CH 2CH 2CF 3
A-122	CH 2CH 2CH 2CH 2CH 2CH 2CCl 3
		A-123	CF 2CF 2CF 2CF 2CF 2CF 2CF 3
A-124	CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 3
		A-125	CH(CH 3)CH 2CH 2CH 2CH 2CH 2F
A-126	CH(CH 3)CH 2CH 2CH 2CH 2CH 2Cl
		A-127	CH(CH 3)CH 2CH 2CH 2CH 2CF 3
A-128	CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-129	CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-130	CH 2CHFCH 2CH 2CH 2CH 2CH 2CH 3
		A-131	CH 2CHClCH 2CH 2CH 2CH 2CH 2CH 3
A-132	CH 2CH 2CHFCH 2CH 2CH 2CH 2CH 3
		A-133	CH 2CH 2CHClCH 2CH 2CH 2CH 2CH 3
A-134	CH 2CH 2CH 2CH 2CHFCH 2CH 2CH 3
		A-135	CH 2CH 2CH 2CH 2CHClCH 2CH 2CH 3
A-136	CH 2CH 2CH 2CH2CH 2CHFCH 2CH 3
		A-137	CH 2CH 2CH 2CH 2CH 2CHClCH 2CH 3
A-138	CH 2CH 2CH 2CH 2CH 2CH 2CHFCH 3
		A-139	CH 2CH 2CH 2CH 2CH 2CH 2CHClCH 3
A-140	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2F
		A-141	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2Cl
A-142	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-143	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-144	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHF 2
		A-145	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHCl 2
A-146	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CF 3
		A-147	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CCl 3
A-148	CF 2CF 2CF 2CF 2CF2CF 2CF 2CF 3
		A-149	CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 3
A-150	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2F

Sequence number	R 1
		A-151	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2Cl
A-152	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CF 3
		A-153	CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-154	CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-155	CH 2CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-156	CH 2CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-157	CH 2CH 2CHFCH 2CH 2CH 2CH 2CH 2CH 3
A-158	CH 2CH 2CHClCH 2CH 2CH 2CH 2CH 2CH 3
		A-159	CH 2CH 2CH 2CHFCH 2CH 2CH 2CH 2CH 3
A-160	CH 2CH 2CH 2CHClCH 2CH 2CH 2CH 2CH 3
		A-161	CH 2CH 2CH 2CH 2CH 2CHFCH 2CH 2CH 3
A-162	CH 2CH 2CH 2CH 2CH 2CHClCH 2CH 2CH 3
		A-163	CH 2CH 2CH 2CH 2CH 2CH 2CHFCH 2CH 3
A-164	CH 2CH 2CH 2CH 2CH 2CH 2CHClCH 2CH 3
		A-165	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHFCH 3
A-166	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHClCH 3
		A-167	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2F
A-168	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2Cl
		A-169	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-170	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-171	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHF 2
A-172	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHCl 2
		A-173	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CF 3
A-174	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CCl 3
		A-175	CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3
A-176	CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 3
		A-177	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CH 2F
A-178	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CH 2Cl
		A-179	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CF 3
A-180	CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-181	CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-182	CH 2CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-183	CH 2CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-184	CH 2CH 2CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-185	CH 2CH 2CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-186	CH 2CH 2CH 2CHFCH 2CH 2CH 2CH 2CH 2CH 3
		A-187	CH 2CH 2CH 2CHClCH 2CH 2CH 2CH 2CH 2CH 3
A-188	CH 2CH 2CH 2CH 2CHFCH 2CH 2CH 2CH 2CH 3

Sequence number	R 1
		A-189	CH 2CH 2CH 2CH 2CHClCH 2CH 2CH 2CH 2CH 3
A-190	CH 2CH 2CH 2CH 2CH 2CH 2CHFCH 2CH 2CH 3
		A-191	CH 2CH 2CH 2CH 2CH 2CH 2CHClCH 2CH 2CH 3
A-192	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHFCH 2CH 3
		A-193	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHClCH 2CH 3
A-194	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHFCH 3
		A-195	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHClCH 3
A-196	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2F
		A-197	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2Cl
A-198	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-199	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-200	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHF 2
		A-201	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CHCl 2
A-202	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CF 3
		A-203	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CCl 3
A-204	CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3
		A-205	CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 2CCl 3
A-206	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2F
		A-207	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2Cl
A-208	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CH 2CF 3
		A-209	CH＝CH 2
A-210	CH 2CH＝CH 2
		A-211	CH＝CHCH 3
A-212	C(CH 3)＝CH 2
		A-213	CH 2CH 2CH＝CH 2
A-214	CH 2CH＝CHCH 3
		A-215	CH＝CHCH 2CH 3
A-216	CH(CH 3)CH＝CH 2
		A-217	C(CH 3)＝CHCH 3
A-218	CH＝C(CH 3) 2
		A-219	CH 2CH 2CH 2CH＝CH 2
A-220	CH 2CH 2CH＝CHCH 3
		A-221	CH 2CH＝CHCH 2CH 3
A-222	CH＝CHCH 2CH 2CH 3
		A-223	CH(CH 3)CH 2CH＝CH 2
A-224	CH 2C(CH 3)＝CHCH 3

Sequence number	R 1
		A-225	CH 2CH＝C(CH 3) 2
A-226	CH 2CH 2CH 2CH 2CH＝CH 2
		A-227	CH 2CH 2CH 2CH＝CHCH 3
A-228	CH 2CH 2CH＝CHCH 2CH 3
		A-229	CH 2CH＝CHCH 2CH 2CH 3
A-230	CH＝CHCH 2CH 2CH 2CH 3
		A-231	CH(CH 3)CH 2CH 2CH＝CH 2
A-232	CH(CH 3)CH 2CH＝CHCH 3
		A-233	CH 2C(CH 3)＝CHCH 2CH 3
A-234	CH 2CH 2CH＝C(CH 3) 2
		A-235	CH 2CH 2CH 2CH 2CH 2CH＝CH 2
A-236	CH 2CH 2CH 2CH 2CH＝CHCH 3
		A-237	CH 2CH 2CH 2CH＝CHCH 2CH 3
A-238	CH 2CH 2CH＝CHCH 2CH 2CH 3
		A-239	CH 2CH＝CHCH 2CH 2CH 2CH 3
A-240	CH＝CHCH 2CH 2CH 2CH 2CH 3
		A-241	CH(CH 3)CH 2CH 2CH 2CH＝CH 2
A-242	CH(CH 3)CH 2CH 2CH＝CHCH 3
		A-243	C(CH 3)＝CHCH 2CH 2CH 2CH 3
A-244	CH 2CH 2CH 2CH＝C(CH 3) 2
		A-245	CH 2CH 2CH 2CH 2CH 2CH 2CH＝CH 2
A-246	CH 2CH 2CH 2CH 2CH 2CH＝CHCH 3
		A-247	CH 2CH 2CH 2CH 2CH＝CHCH 2CH 3
A-248	CH 2CH 2CH 2CH＝CHCH 2CH 2CH 3
		A-249	CH 2CH 2CH＝CHCH 2CH 2CH 2CH 3
A-250	CH 2CH＝CHCH 2CH 2CH 2CH 2CH 3
		A-251	CH＝CHCH 2CH 2CH 2CH 2CH 2CH 3
A-252	CH(CH 3)CH 2CH 2CH 2CH 2CH＝CH 2
		A-253	CH(CH 3)CH 2CH 2CH 2CH＝CHCH 3
A-254	C(CH 3)＝CHCH 2CH 2CH 2CH 2CH 3
		A-255	CH 2CH 2CH 2CH 2CH＝C(CH 3) 2
A-256	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH＝CH 2
		A-257	CH 2CH 2CH 2CH 2CH 2CH 2CH＝CHCH 3
A-258	CH 2CH 2CH 2CH 2CH 2CH＝CHCH 2CH 3

Sequence number	R 1
		A-259	CH 2CH 2CH 2CH 2CH＝CHCH 2CH 2CH 3
A-260	CH 2CH 2CH 2CH＝CHCH 2CH 2CH 2CH 3
		A-261	CH 2CH 2CH＝CHCH 2CH 2CH 2CH 2CH 3
A-262	CH 2CH＝CHCH 2CH 2CH 2CH 2CH 2CH 3
		A-263	CH＝CHCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-264	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH＝CH 2
		A-265	CH(CH 3)CH 2CH 2CH 2CH 2CH＝CHCH 3
A-266	C(CH 3)＝CHCH 2CH 2CH 2CH 2CH 2CH 3
		A-267	CH 2CH 2CH 2CH 2CH 2CH＝C(CH 3) 2
A-268	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH＝CH 2
		A-269	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH＝CHCH 3
A-270	CH 2CH 2CH 2CH 2CH 2CH 2CH＝CHCH 2CH 3
		A-271	CH 2CH 2CH 2CH 2CH 2CH＝CHCH 2CH 2CH 3
A-272	CH 2CH 2CH 2CH 2CH＝CHCH 2CH 2CH 2CH 3
		A-273	CH 2CH 2CH 2CH＝CHCH 2CH 2CH 2CH 2CH 3
A-274	CH 2CH 2CH＝CHCH 2CH 2CH 2CH 2CH 2CH 3
		A-275	CH 2CH＝CHCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-276	CH＝CHCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-277	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2CH＝CH 2
A-278	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH＝CHCH 3
		A-279	C(CH 3)＝CHCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-280	CH 2CH 2CH 2CH 2CH 2CH 2CH＝C(CH 3) 2
		A-281	C≡CH
A-282	CH 2C≡CH
		A-283	C≡CCH 3
A-284	CH 2CH 2C≡CH
		A-285	CH 2C≡CCH 3
A-286	C≡CCH 2CH 3
		A-287	CH(CH 3)C≡CH
A-288	CH 2CH 2CH 2C≡CH
		A-289	CH 2CH 2C≡CCH 3
A-290	CH 2C≡CCH 2CH 3
		A-291	C≡CCH 2CH 2CH 3
A-292	CH(CH 3)CH 2C≡CH

Sequence number	R 1
		A-293	CH 2CH 2CH 2CH 2C≡CH
A-294	CH 2CH 2CH 2C≡CCH 3
		A-295	CH 2CH 2C≡CCH 2CH 3
A-296	CH 2C≡CCH 2CH 2CH 3
		A-297	C≡CCH 2CH 2CH 2CH 3
A-298	CH(CH 3)CH 2CH 2C≡CH
		A-299	CH(CH 3)CH 2C≡CCH 3
A-300	CH 2CH 2CH 2CH 2CH 2C≡CH
		A-301	CH 2CH 2CH 2CH 2C≡CCH 3
A-302	CH 2CH 2CH 2C≡CCH 2CH 3
		A-303	CH 2CH 2C≡CCH 2CH 2CH 3
A-304	CH 2C≡CCH 2CH 2CH 2CH 3
		A-305	C≡CCH 2CH 2CH 2CH 2CH 3
A-306	CH(CH 3)CH 2CH 2CH 2C≡CH
		A-307	CH(CH 3)CH 2CH 2C≡CCH 3
A-308	CH(CH 3)CH 2C≡CCH 2CH 3
		A-309	CH 2CH 2CH 2CH 2CH 2CH 2C≡CH
A-310	CH 2CH 2CH 2CH 2CH 2C≡CCH 3
		A-311	CHxCH 2CH 2CH 2C≡CCH 2CH 3
A-312	CH 2CH 2CH 2C≡CCH 2CH 2CH 3
		A-313	CH 2CH 2C≡CCH 2CH 2CH 2CH 3
A-314	CH 2C≡CCH 2CH 2CH 2CH 2CH 3
		A-315	C≡CCH 2CH 2CH 2CH 2CH 2CH 3
A-316	CH(CH 3)CH 2CH 2CH 2CH 2C ≡CH
		A-317	CH(CH 3)CH 2CH 2CH 2C≡CCH 3
A-318	CH 2CH 2CH 2CH 2CH 2CH 2CH 2C≡CH
		A-319	CH 2CH 2CH 2CH 2CH 2CH 2C≡CCH 3
A-320	CH 2CH 2CH 2CH 2CH 2C≡CCH 2CH 3
		A-321	CH 2CH 2CH 2CH 2C≡CCH 2CH 2CH 3
A-322	CH 2CH 2CH 2C≡CCH 2CH 2CH 2CH 3
		A-323	CH 2CH 2C≡CCH 2CH 2CH 2CH 2CH 3
A-324	CH 2C≡CCH 2CH 2CH 2CH 2CH 2CH 3
		A-325	C≡CCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-326	CH(CH 3)CH 2CH 2CH 2CH 2CH 2C≡CH

Sequence number	R 1
		A-327	CH(CH 3)CH 2CH 2CH 2CH 2C≡CCH 3
A-328	CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2C≡CH
		A-329	CH 2CH 2CH 2CH 2CH 2CH 2CH 2C≡CCH 3
A-330	CH 2CH 2CH 2CH 2CH 2CH 2C≡CCH 2CH 3
		A-331	CH 2CH 2CH 2CH 2CH 2C≡CCH 2CH 2CH 3
A-332	CH 2CH 2CH 2CH 2C≡CCH 2CH 2CH 2CH 3
		A-333	CH 2CH 2CH 2C≡CCH 2CH 2CH 2CH 2CH 3
A-334	CH 2CH 2C≡CCH 2CH 2CH 2CH 2CH 2CH 3
		A-335	CH 2C≡CCH 2CH 2CH 2CH 2CH 2CH 2CH 3
A-336	C≡CCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
		A-337	CH(CH 3)CH 2CH 2CH 2CH 2CH 2CH 2C≡CH
A-338	CH(CH 3)CH 2CH 2CH 2CH 2CH 2C≡CCH 3
		A-339	CHFCH 2CN
A-340	CHClCH 2CN
		A-341	CCl 2CH 2CN
A-342	CF 2CH 2CN
		A-343	CHFCH 2CH 2CN
A-344	CHClCH 2CH 2CN
		A-345	CCl 2CH 2CH 2CN
A-346	CF 2CH 2CH 2CN
		A-347	CHFCH 2CH 2CH 2CN
A-348	CHClCH 2CH 2CH 2CN
		A-349	CCl 2CH 2CH 2CH 2CN
A-350	CF 2CH 2CH 2CH 2CN
		A-351	CHFCH 2CH 2CH 2CH 2CN
A-352	CHClCH 2CH 2CH 2CH 2CN
		A-353	CCl 2CH 2CH 2CH 2CH 2CN
A-354	CF 2CH 2CH 2CH 2CH 2CN
		A-355	CHFCH 2CH 2CH 2CH 2CH 2CN
A-356	CHClCH 2CH 2CH 2CH 2CH 2CN
		A-357	CCl 2CH 2CH 2CH 2CH 2CH 2CN
A-358	CF 2CH 2CH 2CH 2CH 2CH 2CN
		A-359	CHFCH 2CH 2CH 2CH 2CH 2CH 2CN
A-360	CHClCH 2CH 2CH 2CH 2CH 2CH 2CN
		A-361	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-362	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CN

Sequence number	R 1
		A-363	CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-364	CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
		A-365	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-366	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
		A-367	CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-368	CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
		A-369	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-370	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
		A-371	CHFCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-372	CHClCH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
		A-373	CCl 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN
A-374	CF 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CN

Compound I is suitable for as mycocide.They have significant effectiveness to the plant pathogenic fungi of wide region, described fungi especially is selected from Ascomycetes (Ascomycetes), deuteromycetes (Deuteromycetes), Oomycete (Oomycetes) and Basidiomycetes (Basidiomycetes) fungi, especially Oomycete fungi.Inhale in them some effectively and can be used as blade face mycocide and soil mycocide is used for plant protection.

They are even more important to a large amount of fungies of control in the seed of various cultivated plants such as wheat, rye, barley, oat, rice, corn, dogstail, banana, cotton, soybean, coffee, sugarcane, grape vine, fruit and ornamental plant and vegetables such as cucumber, beans, tomato, potato and cucurbitaceous plant and these plants.

They are particularly suited for preventing and treating the following plants disease:

Chain lattice spore (Alternaria) on-vegetables, Semen Brassicae campestris, sugar beet, fruit and the rice belongs to (for example epidemic disease chain lattice spores morning (A.solani) on potato and the other plant or alternaria (A.alternata)),

Silk capsule mould (Aphanomyces) on-sugar beet and the vegetables belongs to,

Flat navel in-corn, cereal class, rice and the lawn wriggles that spore (Bipolaris) belongs to and interior navel is wriggled, and spore (Drechslera) belongs to (for example the interior navel of the barley filigree on the barley spore (D.teres) of wriggling, the D.tritci-repentis on the wheat),

Standing grain powdery mildew in the-cereal class (Blumeria graminis) (Powdery Mildew),

Botrytis cinerea on-strawberry, vegetables, flowers and the grape vine (Botrytis cinerea) (gray mold),

Lettuce dish stalk mould (Bremia lactucae) on-lettuce,

Tail spore (Cercospora) on-corn, soybean, rice and the sugar beet belongs to (for example C.beticula on the sugar beet),

Cochliobolus (Cochliobolus) on-corn, cereal class, the rice belongs to (for example the standing grain cochliobolus on the cereal class (Cochliobolus sativus), the palace portion cochliobolus (Cochliobolusmiyabeanus) on the rice),

Perverse dish spore (Colletotricum) on-soybean, cotton and the other plant belongs to (for example C.acutatum on each kind of plant),

Prominent navel on the-corn spore (Exserohilum) of wriggling belongs to,

Two spore powdery mildews (Erysiphe cichoracearum) on-cucurbitaceous plant and monofilament shell powdery mildew (Sphaerotheca fuliginea),

Fusarium (Fusarium) on-each kind of plant belongs to (for example Fusarium graminearum on the wheat (F.graminearum)) and wheel branch spore (Verticillium) belongs to (for example big beautiful Verticillium (V.dahliae)),

Gaeumannomyce on the-cereal class (Gaeumanomyces graminis) belongs to,

Red mould (Gibberella) on-cereal class and the rice belongs to (for example gibberella fujikuroi on the rice (Gibberellafujikuroi)),

Grainstaining complex on the-rice,

Length on-corn and the rice spore (Helminthosporium) of wriggling belongs to (for example H.graminicola),

Michrodochium nivale on the-cereal class,

Ball chamber bacterium (Mycosphaerella) on-cereal class, banana and the peanut belongs to (the standing grain green-ball chamber bacterium (M.graminicola) on the wheat, the M.fijiesis on the banana),

Yam bean layer rest fungus (Phakopsora pachyrhizi) on-soybean and mountain horseleech layer rest fungus (Phakopsara meibomiae),

Phomopsis on-soybean, Sunflower Receptacle and the grape vine (Phomopsis) belongs to (the grape Phomopsis (P.viticola) on the grape vine, the P.helianthii on the Sunflower Receptacle),

Phytophthora infestans on-potato and the tomato (Phytophthora infestans),

Grape on the-grape vine is given birth to single shaft mould (Plasmopara viticola),

Apple mildew bacterium on the-apple (Podosphaera leucotricha),

The rotten germ (Pseudocercosporella herpotrichoides) of wheat-based on the-cereal class,

False downy mildew (Pseudoperonospora) on-hops and the cucurbitaceous plant belongs to (for example P.cubenis on the cucumber),

Handle rest fungus (Puccinia) on-cereal class, corn and the asparagus belongs to (wheat rust on the wheat (P.triticina) and stripe rust (P.striformis), the asparagus rust (P.asparagi) on the asparagus),

Nuclear cavity bacteria on the-cereal class (Pyrenophora) belongs to,

Pyricularia oryzae on the-rice (Pyricularia oryzae), Bamboo grass wood photovoltaicing leather bacteria (Corticium sasakii), broom stalk Cylindrocarpon (Sarocladium oryzae), sheath rot of rice plant (S.attenuatum), rice leaf ustilago (Entyloma oryzae)

Piricularia oryzae on-lawn and the cereal class (Pyricularia grisea),

Rotten mould (Pythium) on-lawn, rice, corn, cotton, Semen Brassicae campestris, Sunflower Receptacle, sugar beet, vegetables and the other plant belongs to,

Rhizoctonia on-cotton, rice, potato, lawn, corn, Semen Brassicae campestris, sugar beet, vegetables and the other plant (Rhizoctonia) belongs to (for example miliary damping-off germ (R.solani)),

Sclerotinite on-Semen Brassicae campestris, Sunflower Receptacle and the other plant (Sclerotinia) belongs to (for example sclerotinite (S.sclerotiorum)),

Wheat septoria on the-wheat (Septoria tritici) and the many spores of clever withered shell (Stagonosporanodorum),

Grape snag shell on the-grape vine (Erysiphe (synonym Uncinula necator),

Setospaeria on-corn and the lawn belongs to,

Silk axle ustilago (Sphacelotheca reilinia) on-corn,

Thielaviopsis sp on-soybean and the cotton (Thievaliopsis) belongs to,

Tilletia foetida on the-cereal class (Tilletia) belongs to,

Ustilago on-cereal class, corn and the sugar beet (Ustilago) belongs to, and

Black star bacterium (Venturia) on-apple and the pears belongs to (black spot) (for example scab of apple on the apple (V.inaequalis)).

They are particularly suitable for control and are selected from Oomycete, as the harmful fungoid that downy mildew (Peronospora) belongs to, epidemic disease mould (Phytophthora) belongs to, grape is given birth to the mould and false Peronospora of single shaft.

In addition, Compound I also is suitable for preventing and treating the product of harmful fungoid with protecting materials (as timber, paper, lacquer dispersion, fiber or fabric) and protection storage.In wood protection, should note following harmful fungoid especially: the Ascomycetes fungi, belong to (Ophiostoma spp.) as line mouth shell, long beak shell belongs to (Ceratocystis spp.), Aureobasidium pullulans (Aureobasidium pullulans), Sclerophomaspp., Chaetomium (Chaetomium spp.), Humicola (Humicola spp.), Peter's shell belongs to (Petriella spp.), the mould genus of pieces (Trichurus spp.); The Basidiomycetes fungi; belong to (Coniophora spp.) as cellar fungus; Coriolus Qu61 (Coriolus spp.); sticking gill fungus belongs to (Gloeophyllumspp.); Lentinus (Lentinus spp.); pleurotus (Pleurotus spp.); transverse hole fungus belongs to (Poriaspp.); Merulius (Serpula spp.) and cheese Pseudomonas (Tyromyces spp.); the deuteromycetes fungi; as Aspergillus (Aspergillus spp.); Cladosporium (Cladosporium spp.); Penicillium (Penicillium spp.); Trichoderma (Trichoderma spp.), Alternaria (Alternaria spp.), paecilomyces (Paecilomyces spp.) and zygomycetes (Zygomycetes) fungi; as Mucor (Mucor spp.), in material protection, additionally should note following yeast: mycocandida (Candidaspp.) and yeast saccharomyces cerevisiae (Saccharomyces cerevisae).

Compound I can need maybe to prevent that plant, seed, material or the soil of fungal attack from using by handling fungi with the active compound of fungicidal significant quantity.Use and before material, plant or seed are by fungal infection and afterwards, to carry out.

Fungicide composition comprises 0.1-95 weight % usually, the active compound of preferred 0.5-90 weight %.

When being used for plant protection, amount of application depends on that the kind of required effect is 0.01-2.0kg active compound/hectare.

In seed treatment, the active compound amount that every 100kg seed requires usually is 1-1000g, preferred 5-100g.

When being used for protecting materials or storage product, the amount of application of active compound depends on type and the required effect of using the zone.The for example every m of the amount of in protecting materials, using usually ³The processing material is 0.001g-2kg, preferred 0.005g-1kg active compound.

Formula I compound can exist by the different crystal formation of various biological activitys possibilities.They also form the part of theme of the present invention.

Compound I can be changed into conventional preparaton, for example solution, emulsion, suspension, pulvis, powder, paste and particle.Administration form depends on specific purpose; All should guarantee the meticulous and distribution equably of The compounds of this invention in each case.

Preparaton prepares in a known way, for example prepares by active compound is mixed with solvent and/or carrier, if the words that need are used emulsifying agent and dispersion agent.Suitable solvent/auxiliary agent is mainly:

-water, aromatic solvent (as Solvesso product, dimethylbenzene), paraffin (as mineral oil fractions), alcohols (as methyl alcohol, butanols, amylalcohol, benzylalcohol), ketone (as pimelinketone, gamma-butyrolactone), pyrrolidone (NMP, NOP), acetic ester (glycol diacetate), dibasic alcohol, lipid acid dimethylformamide, lipid acid and fatty acid ester.Can also use solvent mixture in principle.

-carrier such as ground natural mineral (as kaolin, clay, talcum, chalk) and ground synthetic mineral (as silica, the silicate of high dispersing); Emulsifying agent such as nonionic and anionic emulsifier (as polyoxyethylene aliphatic alcohol ether, alkylsulfonate and arylsulphonate) and dispersion agent such as lignin sulfite waste lye and methylcellulose gum.

Suitable tensio-active agent is a lignosulfonic acid, naphthene sulfonic acid, sulfocarbolic acid, the an alkali metal salt of dibutyl naphthene sulfonic acid, alkaline earth salt and ammonium salt, alkylaryl sulphonate, alkyl-sulphate, alkylsulfonate, aliphatic alcohol sulfate, lipid acid and sulphated fatty alcohol glycol ether, also have sulfonated naphthalene and the condenses of formaldehyde and the condenses of naphthalene derivatives and formaldehyde, the condenses of naphthalene or naphthene sulfonic acid and phenol and formaldehyde, polyoxyethylene octylphenol ether, the ethoxylation isooctylphenol, octyl phenol, nonyl phenol, alkyl phenol polyoxyethylene glycol ether, tributyl phenyl polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, pure and mild Fatty Alcohol(C12-C14 and C12-C18)/ethylene oxide condenses, ethoxylated castor oil, Voranol EP 2001, ethoxylation polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste lye and methylcellulose gum.

In being suitable for preparing the direct material of spray solution, emulsion, paste or oil dispersion and being to mineral oil fractions such as the kerosene or the diesel oil of high boiling point, the oil that also has coal tar and plant or animal-origin, aliphatic series, ring-type and aromatic hydrocarbon such as toluene, dimethylbenzene, paraffin, tetraline, alkylated naphthalene or derivatives thereof, methyl alcohol, ethanol, propyl alcohol, butanols, hexalin, pimelinketone, isophorone, intensive polar solvent such as methyl-sulphoxide, N-Methyl pyrrolidone and water.

But powder, broadcast sowing with material and dusting product and can prepare by active substance is mixed or grinds with solid carrier.

Particle such as coating particle, impregnated granules and homogeneous particle can prepare by active compound and solid carrier are adhered to.The solid carrier example is that ore deposit soil is as silica gel, silicate, talcum, kaolin, activated clay (attaclay), Wingdale, lime, chalk, terra miraculosa, loess, clay, rhombspar, diatomite, calcium sulfate, sal epsom, magnesium oxide, the ground synthetic materials, the product of fertilizer such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and plant origin such as flour, tree bark powder, wood powder and nutshell powder, cellulose powder and other solid carrier.

Preparaton comprises 0.01-95 weight % usually, the active compound of preferred 0.1-90 weight %.Active compound is with 90-100%, and the purity of preferred 95-100% (according to the NMR spectrum) is used.

Under classify the preparaton example as:

1. the product of dilute with water

A) water-soluble concentrate (SL, LS)

10 weight part active compounds are dissolved in 90 weight parts waters or the water-soluble solvent.Perhaps, add wetting agent or other auxiliary agent.Active compound is through water dilution dissolving.Obtain the preparaton that active compound content is 10 weight % in this way.

B) dispersed enriched material (DC)

Be dissolved in 20 weight part active compounds in the 70 weight part pimelinketone and add 10 weight part dispersion agent such as Polyvinylpyrolidone (PVP)s.Dilute with water obtains dispersion.Active compound content is 20 weight %.

C) missible oil (EC)

Be dissolved in 15 weight part active compounds in the 75 weight part dimethylbenzene and add calcium dodecylbenzene sulphonate and castor oil ethoxylate (being 5 weight parts in each case).Dilute with water obtains emulsion.The active compound content of this preparaton is 15 weight %.

D) emulsion (EW, EO, ES)

Be dissolved in 25 weight part active compounds in the 35 weight part dimethylbenzene and add calcium dodecylbenzene sulphonate and castor oil ethoxylate (being 5 weight parts in each case).Add this mixture in 30 weight parts waters and make equal phase emulsion by mulser (for example Ultraturrax).Dilute with water obtains emulsion.The active compound content of this preparaton is 25 weight %.

E) suspension (SC, OD, FS)

In the ball mill that stirs, 20 weight part active compounds are pulverized and added 10 weight part dispersion agents and wetting agent and 70 weight parts waters or organic solvent, obtain active compound suspension in small, broken bits.Dilute with water obtains stable active compound suspension.Active compound content in this preparaton is 20 weight %.

F) water-dispersible granule and water-soluble granular (WG, SG)

With the grinding in small, broken bits of 50 weight part active compounds and add 50 weight part dispersion agent and wetting agents, be made into water dispersible or water-soluble granular by full scale plant (as forcing machine, spray tower, fluidized-bed).Dilute with water obtains stable active compound dispersion or solution.The active compound content of this preparaton is 50 weight %.

G) water dispersible pow-ders and water-soluble powder (WP, SP, SS, WS)

75 weight part active compounds are ground in the rotor-stator grinding machine and add 25 weight part dispersion agents, wetting agent and silica gel.Dilute with water obtains stable active compound dispersion or solution.The active compound content of this preparaton is 75 weight %.

H) gel formulation

In ball mill, 20 weight part active compounds, 10 weight part dispersion agents, 1 weight part jelling agent and 70 weight parts waters or organic solvent grinding are obtained finely divided suspension.Dilute with water obtains the stable suspension that active compound content is 20 weight %.

2. the product of using without dilution

I) but dusting powder (DP, DS)

With the grinding in small, broken bits of 5 weight part active compounds and with 95 weight parts kaolin thorough mixing in small, broken bits.But this obtains the dusting product that active compound content is 5 weight %.

J) particle (GR, FG, GG, MG)

With the grinding in small, broken bits of 0.5 weight part active compound and in conjunction with 99.5 weight part carriers.Current methods be extrude, spraying drying or bed process.The active compound content that this obtains using without dilution is the particle of 0.5 weight %.

K) ULV solution (UL)

10 weight part active compounds are dissolved in 90 weight part organic solvents such as the dimethylbenzene.The active compound content that this obtains using without dilution is the product of 10 weight %.

Seed treatment is utilized water-soluble concentrate (LS), suspension (FS) but dusting powder (DS), water dispersible and water-soluble powder (WS, SS), emulsion (ES), missible oil (EC) and gel formulation (GF) usually.These preparatons can not diluted or preferred dilution after be applied on the seed.Use and to carry out prior to seeding.

Active compound can be directly, with its preparaton form or type of service prepared therefrom (but as directly spray solution, powder, suspension or dispersion, emulsion, oil dispersion, paste dusting product, broadcast sowing), by spraying, atomizing, dusting, broadcast sowing or water and use with material or particle.Type of service depends on the purpose that is intended to fully; They should guarantee the best fine distribution of active compound of the present invention in each case.

Moisture type of service can be prepared by emulsion concentrates, paste or wettable powder (sprayable powder, oil dispersion) by adding entry.Be preparation emulsion, paste or oil dispersion, can be with this material directly or be dissolved in back homogenizing in water in oil or the solvent by wetting agent, tackifier, dispersion agent or emulsifying agent.Perhaps can also prepare enriched material and this enriched material formed by active substance, wetting agent, tackifier, dispersion agent or emulsifying agent and suitable solvent or oil and be suitable for dilute with water.

Active compound can change in relative broad range with the concentration in the preparation shortly.They are generally 0.0001-10%, preferred 0.01-1%.

Active compound also can successfully use with ultra-low volume method (ULV), wherein can use to comprise the preparaton that surpasses 95 weight % active compounds or even can not have to use active compound under the situation of additive.

Various types of oil, wetting agent, auxiliary, weedicide, mycocide, other agricultural chemicals or sterilant can be added in the active compound just (bucket mixes) adding before being close to use of suitable words.These reagent can 1: 100-100: 1, preferred 1: 10-10: 1 weight ratio and reagent mix of the present invention.

In this respect and stark suitable auxiliary especially is organically-modified polysiloxane, for example BreakThru S 240 ^Alcohol alkoxylate, for example Atplus 245 ^, Atplus MBA 1303 ^, Plurafac LF 300 ^With Lutensol ON 30 ^The EO/PO block polymer, for example PluronicRPE 2035 ^With Genapol B ^Alcohol ethoxylate, for example Lutensol XP 80 ^And Sodium docusate, for example Leophen RA ^

In the type of service as mycocide, the present composition also can exist with other active compound, for example exists with weedicide, sterilant, growth regulator, mycocide or fertilizer.In the time of will mixing as Compound I or the composition that comprises them and other active compound, the especially mycocide that mycocide is used, can widen activity profile in many cases or prevent drug-fast generation.Obtained cooperative synergism effect in many cases.

The following mycocide that The compounds of this invention can be used in combination with it is used for illustrating possible combination but does not limit them:

Strobilurins class (Strobilurins)

-nitrile Azoxystrobin (azoxystrobin), ether bacterium amine (dimoxystrobin), enostroburin (enestroburin), fluoxastrobin (fluoxastrobin), imines bacterium (kresoxim-methyl), fork phenalgin acid amides (metominostrobin), ZEN 90160 (picoxystrobin), Strobilurin (pyraclostrobin), oxime bacterium ester (trifloxystrobin), orysastrobin (orysastrobin), (2-chloro-5-[1-(3-methyl benzyloxy imino) ethyl] benzyl) Urethylane, (2-chloro-5-[1-(6-picoline-2-ylmethoxy imino-) ethyl] benzyl) Urethylane, 2-(neighbour-((2,5-dimethyl phenoxy methylene radical) phenyl)-3-methoxy-methyl acrylate;

Carboxyl acylamide

-carboxylic acylaniline class: M 9834 (benalaxyl), benodanil (benodanil), boscalid amine (boscalid), carboxin (carboxin), third oxygen goes out and embroiders amine (mepronil), methuroxam (fenfuram), fenhexamid (fenhexamid), fultolanil (flutolanil), furan pyrazoles spirit (furametpyr), metaxanin (metalaxyl), fenfuram (ofurace),  frost spirit (oxadixyl), oxycarboxin (oxycarboxin), pyrrole metsulfovax (penthiopyrad), thifluzamide (thifluzamide), tiadinil (tiadinil), N-(4 '-bromo biphenyl-2-yl)-4-difluoromethyl-2-methylthiazol-5-methane amide, N-(4 '-trifluoromethyl-biphenyl-2-yl)-4-difluoromethyl-2-methylthiazol-5-methane amide, N-(4 '-chloro-3 '-fluorine biphenyl-2-yl)-4-difluoromethyl-2-methylthiazol-5-methane amide, N-(3 ', 4 '-two chloro-4-fluorine biphenyl-2-yls)-3-difluoromethyl-1-methylpyrazole-4-methane amide, N-(2-cyano-phenyl)-3,4-two chloroisothiazoles-5-methane amide;

-carboxylic acid morpholine thing: dimethomorph (dimethomorph), flumorph (flumorph);

-benzamides: fluorine biphenyl bacterium (flumetover), fluopicolide (fluorine pyrrole bacterium amine (picobenzamid)), zoxamide (zoxamide);

-other carboxylic acid amides: carpropamide (carpropamid), two chlorine zarilamid (diclocymet), mandipropamid amine (mandipropamid), N-(2-(4-[3-(4-chloro-phenyl-) third-2-alkynyloxy group]-3-p-methoxy-phenyl) ethyl)-2-methane sulfonyl amino-3-methylbutyryl amine, N-(2-(4-[3-(4-chloro-phenyl-) third-2-alkynyloxy group]-the 3-p-methoxy-phenyl) ethyl)-2-ethane sulfuryl amino-3-methylbutyryl amine; Azole

-triazole species: Bitertanol (bitertanol), bromuconazole (bromuconazole), cyproconazole (cyproconazole),  ether azoles (difenoconazole), alkene azoles alcohol (diniconazole), IMAZALIL (enilconazole), oxole bacterium (epoxiconazole), RH-7592 (fenbuconazole), fluzilazol (flusilazole), Fluquinconazole (fluquinconazole), flutriafol (flutriafol), own azoles alcohol (hexaconazole), acid amides azoles (imibenconazole), cycltebuconazole (ipconazole), encircle penta azoles bacterium (metconazole), nitrile bacterium azoles (myclobutanil), Topaze (penconazole), Wocosin 50TK (propiconazole), prothioconazoles (prothioconazole), simeconazoles (simeconazole), tebuconazole (tebuconazole), fluorine ether azoles (tetraconazole), Triabimeno I (triadimenol), triazolone (triadimefon), triticonazole (triticonazole);

-imidazoles: cyanogen frost azoles (cyazofamid), IMAZALIL (imazalil), pefurazoate (pefurazoate), Prochloraz (prochloraz), fluorine bacterium azoles (triflumizole);

-benzimidazoles: F-1991 (benomyl), derosal (carbendazim), fuberidazole (fuberidazole), Apl-Luster (thiabendazole);

-other: Guardian (ethaboxam), Truban (etridiazole), hymexazol (hymexazole); The nitrogen heterocyclic ring based compound

-pyridines: fluazinam (fluazinam), pyrifenox (pyrifenox), 3-[5-(4-chloro-phenyl-)-2, the different  azoles alkane of 3-dimethyl-3-yl] pyridine;

-miazines: the phonetic bacterium spirit of sulphur (bupirimate), ring third pyrimidine (cyprodinil), ferimzone (ferimzone), fenarimol (fenarimol), mepanipyrim (mepanipyrim), nuarimol (nuarimol), pyrimethanil (pyrimethanil);

-piperazines: triforine (triforine);

-pyroles: fluorine  bacterium (fludioxonil), fenpiclonil (fenpiclonil);

-morpholine class: 4-dodecyl-2,6-thebaine (aldimorph), dodemorfe (dodemorph), fenpropimorph (fenpropimorph), tridemorph (tridemorph);

-dicarboximide class: different third fixed (iprodione), the sterilization profit (procymidone), vinclozolin (vinclozolin);

-other: thiadiazoles element (acibenzolar-S-methyl), anilazine (anilazine), Vancide 89 (captan), Difolatan (captafol), dazomet (dazomet), diclomezine (diclomezine), zarilamid (fenoxanil), Phaltan (folpet), fenpropidin (fenpropidin),  famoxadone (famoxadone), fenamidone (fenamidone), different thiophene bacterium ketone (octhilinone), thiabendazole (probenazole), the third oxygen quinoline (proquinazid), pyroquilon (pyroquilon), quinoxyfen (quinoxyfen), tricyclazole (tricyclazole), 5-chloro-7-(4-methyl piperidine-1-yl)-6-(2,4, the 6-trifluorophenyl)-[1,2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6-iodo-3-propyl group chromene-4-ketone, N, N-dimethyl-3-(3-bromo-6-fluoro-2 methyl indole-1-alkylsulfonyl)-[1,2,4] triazole-1-sulphonamide;

Carbaminate and dithiocar-bamate

-dithiocarbamate(s): Karbam Black (ferbam), zinc manganese ethylenebisdithiocarbamate (mancozeb), maneb (maneb), Carbatene (metiram), metamsodium (metam), propineb (propineb), thiram (thiram), zineb (zineb), ziram (ziram);

-Carbamates: the mould prestige of second (diethofencarb), flubenthiavalicarb, iprovalicarb (iprovalicarb), hundred dimension spirit (propamocarb), 3-(4-chloro-phenyl-)-3-(different third oxygen carbonylamino of 2--3-methylbutyryl amino) methyl propionates, N-(1-(1-(4-cyano-phenyl) ethane alkylsulfonyl) fourth-2-yl) carboxylamine 4-fluorophenyl ester;

Other mycocides

-guanidine class: dodine (dodine), biguanide spicy acid salt (iminoctadine), Guanoctine (guazatine);

-antibiotics: spring thunder element (kasugamycin), Polyoxin (polyoxins), Streptomycin sulphate (streptomycin), jingganmycin (validamycin A);

-organometallic compound class: triphenyltin salt;

-sulfur heterocyclic ring based compound: isoprothiolane (isoprothiolane), Delan (dithianon);

-organo phosphorous compounds: Hinosan (edifenphos), fosetyl (fosetyl), ethyl phosphine aluminium (fosetyl-aluminum), iprobenfos (iprobenfos), pyrazophos (pyrazophos), tolclofosmethyl (tolclofos-methyl), phosphorous acid and salt thereof;

-organochlorine compound: thiophanate methyl (thiophanate-methyl), m-tetrachlorophthalodinitrile (chlorothalonil), Pecudin (dichlofluanid), tolylfluanid (tolylfluanid), flusulfamide (flusulfamide), phthalide (phthalide), Perchlorobenzene (hexachlorobenzene), pencycuron (pencycuron), quintozene (quintozene);

-nitrophenyl derivative: Niagara 9044 (binapacryl), dinocap (dinocap), dinobuton (dinobuton);

-inorganic active compound: Bordeaux mixture (Bordeaux mixture), neutralized verdigris, copper hydroxide, Cupravit, Basic Chrome Sulphate, sulphur;

-other: the luxuriant amine of spiral shell  (spiroxamine), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), metrafenone (metrafenone).

Synthetic embodiment

The appropriate change initial compounds uses that program prepares other Compound I described in the following synthetic embodiment.The compound that so obtains is in physical data is listed in the table below.

Embodiment 1:2-ethanoyl oneself-preparation of 4-alkynes nitrile

Under 0 ℃, the drips of solution of 22.9g (204mmol) potassium tert.-butoxide in 100ml dimethyl formamide (DMF) be added to 9.0g (97mmol) oneself-5-alkynes nitrile and the solution of 13.9g (97mmol) isobutyl acetate in 150ml DMF in.At first reaction mixture was stirred 30 minutes down at 0 ℃ then, then 20-25 ℃ of following restir 1 hour.Add 100ml water, and with the reaction mixture dichloromethane extraction.After with the dilute hydrochloric acid acidifying, water is extracted with methyl tertiary butyl ether (MTBE).The organic phase water and the NaCl solution washing that merge, dry then.Remove desolvate after, underpressure distillation (0.2 millibar, 70-72 ℃) resistates.Obtain the 7.9g title compound with light yellow liquid.

Embodiment 2:6-fourth-2-alkynyl-2, the preparation of 5-dimethyl pyrazole [1,5-a] pyrimidin-7-yl amine

0.24g (2mmol) was heated 6 hours under refluxing from ketone nitrile, 0.2g (5mmol) 5-methylpyrazole-3-amine and the solution of 0.07g (0.4mmol) tosic acid in the 5ml 1 of embodiment 1.Use MTBE to remove then to desolvate and resistates is dissolved in the methyl alcohol.Crude product uses column chromatography (mobile phase: ethyl acetate) purify.Obtaining the 0.07g fusing point with white crystal is 215-219 ℃ title compound.

¹H NMR[500Mhz]δ：1.7ppm(s，3H)；2.3ppm(s，3H)；2.4ppm(s，3H)；3.5ppm(s，2H)；6.0ppm(s，1H)；7.3ppm(s，2H)。

Table I-Shi I compound

Sequence number	R 1	R 2	R 3	A	Physical data (fusing point [℃]
						I-1	(CH 2) 4CH＝CH 2	CH 3	CH 3	CH	178-179
1-2	CH 2C≡CCH 3	CH 3	CH 3	CH	215-219
						I-3	(CH 2) 4CF＝CF 2	CH 3	CH 3	CH	178-179
I-4	(CH 2) 3CH＝CH 2	CH 3	H	N	242-243

Effect embodiment to harmful fungoid

The fungicidal action of formula I compound is confirmed by following test:

Use solvent/emulsifying agent volume ratio is 99/1 acetone and/or DMSO and emulsifying agent Uniperol ^The mixture of EL (based on the wetting agent with emulsification and dissemination of ethoxylated alkylphenol) is prepared into active compound the stock solution that comprises the 25mg active compound and be made into 10ml.Then this mixture water is made into 100ml.This stock solution is diluted to following activity compound concentration with described solvent/emulsifying agent/water mixture.

Simultaneous test-to the activity of the net blotch of barley that caused by net blotch (Pyrenophora teres), protectiveness was used in 1 day

The leaf of potted plant barley rice shoot is sprayed to the drip point with activity compound concentration aq suspension as described below.Behind dry 24 hours of the spray-painting, with the moisture spore suspension inoculation of test plant with net blotch (Pyrenophora[synonym Drechslera] teres)-net blotch pathogenic agent.Then test plant is put into temperature and is 20-24 ℃ and relatively atmospheric moisture be the greenhouse of 95-100%.The % naked eyes that infect with whole leaf area after 6 days are measured the disease development degree.

Obtain following result with the contrast of immediate prior art:

Application Example 2-in microtitre test to the activity of the pathogenic agent Pyricularia oryzae of rice blast

Active compound is mixed with separately concentration is the stock solution of 10000ppm in DMSO.

This stock solution is moved on to the moisture nutrient media of Fructus Hordei Germinatus base that also is used for fungi in the titer plate (MTP) with transfer pipet be diluted to described activity compound concentration.The moisture spore suspension that adds Pyricularia oryzae then.It is 18 ℃ steam-laden chamber that this plate is placed temperature.Under 405nm, measure MTP at the 7th day use absorption spectrophotometry after the inoculation.

With the growth of parameter of measuring and the control sample that does not conform to active compound and do not conform to fungi and the blank value of active compound compares, to determine the allometry % of pathogenic agent in each active compound.

In this test, the growth of pathogenic agent is suppressed to 23% by 125ppm active compound I-3.

Claims (16)

1. the azoles of formula I and pyrimidine:

Wherein each substituting group is following defines:

R ¹Be C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain is not substituted and maybe can has 1-3 identical or different radicals R ^aAnd/or R ^bOr

Be C ₁-C ₁₄Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₁-C ₆Alkoxy-C ₂-C ₁₂Alkenyl or C ₁-C ₆Alkoxy-C ₂-C ₁₂Alkynyl, wherein carbochain can have 1-3 identical or different radicals R ^a

R ^aBe halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkylthio, C ₃-C ₁₂Alkenyloxy, C ₃-C ₁₂Alkynyloxy group, NR ¹¹R ¹², or

For having 1-4 identical or different radicals R ^bC ₃-C ₆Cycloalkyl;

R ^bBe C ₁-C ₄Alkyl, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₆Alkenyloxy, C ₃-C ₆Alkynyloxy group and NR ¹¹R ¹²,

R ¹¹, R ¹²Be hydrogen or C ₁-C ₆Alkyl;

Radicals R wherein ^aCarbochain itself can be by halo;

R ²Be C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain can be by 1-3 radicals R ^cReplace:

R ^cBe halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₁₂Alkenyloxy, C ₃-C ₁₂Alkynyloxy group, NR ¹¹R ¹²Maybe can have 1-4 identical or different group C ₁-C ₄Alkyl, halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₆Alkenyloxy, C ₃-C ₆Alkynyloxy group or NR ¹¹R ¹²C ₃-C ₆Cycloalkyl;

A is N or CH; With

R ³Be CH ₃And if A is CH, then R ³Extra is hydrogen.

2. according to the formula I compound of claim 1, wherein:

R ¹Be C ₁-C ₁₄Haloalkyl, C ₁-C ₁₂Halogenated alkoxy-C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Haloalkyl, C ₂-C ₁₂Alkenyl, C ₂-C ₁₂Halogenated alkenyl, C ₂-C ₁₂Alkynyl or C ₂-C ₁₂The halo alkynyl, wherein carbochain can have 1-3 radicals R ^a:

R ^aBe cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₁₂Alkenyloxy, C ₃-C ₁₂Alkynyloxy group, NR ¹¹R ¹², or

For having 1-4 identical or different radicals R ^bC ₃-C ₆Cycloalkyl;

R ^bBe C ₁-C ₄Alkyl, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₆Alkenyloxy, C ₃-C ₆Alkynyloxy group and NR ¹¹R ¹²,

R ¹¹, R ¹²Be hydrogen or C ₁-C ₆Alkyl;

Radicals R wherein ^aCarbochain itself can be by halo.

3. according to the formula I compound of claim 1 or 2, wherein:

R ¹Be C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain is not substituted and maybe can has 1-3 identical or different radicals R ^aAnd/or R ^b

4. according to each formula I compound among the claim 1-3, wherein:

R ²Be C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl or C ₂-C ₁₂Alkynyl, wherein carbochain can be by 1-3 radicals R ^cReplace:

R ^cBe cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₁₂Alkenyloxy, C ₃-C ₁₂Alkynyloxy group, NR ¹¹R ¹²Maybe can have 1-4 identical or different group C ₁-C ₄Alkyl, halogen, cyano group, nitro, hydroxyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₃-C ₆Alkenyloxy, C ₃-C ₆Alkynyloxy group or NR ¹¹R ¹²C ₃-C ₆Cycloalkyl.

5. according to each formula I compound among the claim 1-4, wherein R ¹And R ²Have 14 carbon atoms at the most together.

6. according to each formula I compound among the claim 1-5, wherein R ²Be methyl, ethyl or n-propyl.

7. according to each formula I compound among the claim 1-6, wherein A is CH.

8. according to the formula I compound of claim 1, for 6-oneself-5-thiazolinyl-2,5-dimethyl pyrazole [1,5-a] pyrimidin-7-yl amine, 6-fourth-2-alkynyl-2,5-dimethyl pyrazole [1,5-a] pyrimidin-7-yl amine, 2,5-dimethyl-6-(5,6, the 6-trifluoro oneself-the 5-thiazolinyl) pyrazolo [1,5-a] pyrimidin-7-yl amine.

9. method for preparing according to each formula I compound among the claim 1-8 wherein makes the beta-ketoester of formula II:

Wherein R is C ₁-C ₄Alkyl, and the amino azoles reaction of formula III:

Obtain 7-hydroxyl azoles and the pyrimidine of formula IV:

With the halogenation of formula IV compound, obtain formula V compound:

Wherein Hal is a chlorine or bromine, and makes formula V compound and ammonia react.

10. according to the formula IV or the V compound of claim 9.

11. a method for preparing according to each formula I compound among the claim 1-8 wherein makes the acyl cyanide of formula VI:

With amino azoles reaction according to the formula III of claim 9.

12. wherein R who prepares according to claim 1 ¹C for the halogen replacement ₁-C ₁₄Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl or C ₂-C ₁₂The method of the formula I compound of alkynyl, wherein use halide reagent azoles and pyrimidine of halogenation formula VII in the presence of radical initiator or acid:

R wherein ², R ³With A such as claim 1 definition and R be C ₁-C ₁₄Alkyl, C ₁-C ₁₂Alkoxy-C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl, C ₂-C ₁₂Alkynyl, wherein carbochain can have 1-3 the radicals R according to claim 1 ^a

13. a fungicide composition comprises solid or liquid vehicle and according to each formula I compound among the claim 1-8.

14., comprise other active compounds according to the composition of claim 12.

15. seed comprises according to each formula I compound among the claim 1-8 with the amount of 1-1000g/100kg.

16. a method of preventing and treating the plant-pathogenic harmful fungoid, wherein with significant quantity according among the claim 1-8 each formula I compound treatment fungi maybe needs prevent material, plant, soil or the seed of fungal attack.